Reactions of olefin derivatives in the presence of methathesis catalysts

ABSTRACT

The invention provides a method for synthesizing musk macrocycles comprising contacting an easily accessible diene starting materials bearing a Z-olefin moiety and performing a ring closing metathesis reaction in the presence of a Group 8 olefin metathesis catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. § 371) of PCT/EP2019/053336, filed Feb. 11, 2019, which claims benefit of U.S. Application No. 62/629,857, filed February 13, 2018, both of which are incorporated herein by reference in their entirety.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds. Recent advances in applications to organic syntheses and polymer syntheses mostly rely on developments of well-defined olefin metathesis catalysts.

The technology of ruthenium metathesis catalysts has enabled the development of several research platforms including: ring opening metathesis polymerization (ROMP), ring opening cross metathesis (ROCM), cross metathesis (CM), ring closing metathesis (RCM).

In another embodiment, the invention provides methods for the synthesis of macrocyclic compounds utilized in the fragrance industry.

The odor of musk is perhaps the most universally appreciated fragrance. The natural macrocyclic musk compounds turned out to be ketones (animal sources) and lactones (plant materials). They are 15- or 17-membered ring systems. The type of odor is influenced by the ring size. Starting from 14 ring atoms, a weak musk scent is perceived. Compounds with 15-16 ring atoms exhibit strong musk odor.

Macrocyclic musk compounds are expected to be of increasing importance in the future, especially because many of them are naturally occurring and even the synthetic representatives closely resemble the natural counterparts. In addition, the progress in synthetic chemistry contributes to declining prices and will stimulate increased use of this type of musk compounds.

Synthetic musk compounds can be divided into three major classes: aromatic nitro musk compounds, polycyclic musk compounds, and macrocyclic musk compounds. As such, macrocyclic musk compounds have increased in importance in recent years.

The synthesis of macrocyclic musk compounds is difficult, and, in many cases, it is a multi-step procedure. Due to the relatively high production costs, their economic importance is still limited. However, there is a constant demand for these musk compounds in bulk in perfumery industry.

There is a need for effective processes for preparing cyclic compounds based on medium and specifically based on large rings which have at least one keto group. Medium rings generally have 8 to 11 carbon atoms, above 12 carbon atoms one talks of large rings, and compounds based on large rings are also referred to as macrocyclic compounds. Macrocyclic ketones, lactones and epoxides as well as further functionalized macrocycles are aroma chemicals valued in the fragrance industry. There is a need to create new synthetic routes into the highly valued and valuable macrocyclic musk compounds.

The present invention addresses the problems of the prior art and provides an efficient and high-yielding synthesis of macrocyclic musk compounds and their open-chain intermediates, utilizing cross metathesis reactions in the presence of Group 8 metal olefin metathesis catalysts.

The stereochemistry of the alkene, E or Z, in these cyclic structures is often crucial to the biological activity of a molecule or its olfactory characteristics, and small amounts of impurity of the other stereoisomer in chemical mixtures can drastically decrease their potency. It is particularly difficult to separate E- and Z-isomers as techniques for their separation are not general. As such, methods for producing stereochemically pure cyclic compounds are of paramount importance.

Controlling olefin stereochemistry in RCM reactions can be difficult. When using common non-selective metathesis catalysts, selectivity is controlled by the thermodynamic stability of the olefin products and can vary depending on ring size and double bond position.

Furthermore, high catalyst loadings are often needed for macrocyclization reactions using RCM. In these instances, removal of residual metals, the presence of which can be undesirable in the end product or could potentially isomerize products, can be difficult. For some applications, this requires further purification with additives or with multiple chromatographic columns followed by treatment with charcoal.

Common macrocyclic musk compounds include ambrettolide (9-ambrettolide and 7-ambrettolide), nirvanolide, habanolide, cosmone, muscenone, velvione, dihydrocivetone, exaltone, civetone and globanone.

The invention provides a method of forming macrocyclic musk compounds comprising the steps of cross metathesizing a first olefin and a second olefin in the presence of at least one Group 8 metal olefin metathesis catalyst, to form a cross-metathesis product and then cyclizing the cross-metathesis product to form the desired macrocyclic musk compounds.

The macrocyclic musk compounds can be formed by ring closing metathesis of a diene, in the presence of at least one Group 8 metal olefin metathesis catalyst. More particularly the invention is concerned with novel methods for obtaining musk macrocycles in the Z configuration, via cross metathesis reactions, in the presence of at least one Group 8 metal Z-stereoretentive olefin metathesis catalyst.

Using easily accessible diene starting materials bearing a Z-olefin moiety, macrocyclization reactions generated products with significantly higher Z-selectivity in appreciably shorter reaction times, in higher yield, and with much lower catalyst loadings than in previously reported systems. Macrocyclic lactones ranging in size from twelve-membered to seventeen-membered rings are synthesized in moderate to high yields (68-79% yield) with excellent Z-selectivity (95%->99% Z).

SUMMARY OF THE INVENTION Musk Macrocycles

The present invention relates to a process, involving ring closing metathesis in the presence of at least one Group 8 metal olefin metathesis catalyst, for preparing cyclic compounds having at least eight carbon atoms and at least one keto group, used in the fragrance industry.

Ring closing metathesis reactions were achieved, using the catalysts of the invention and it was shown on a variety of substrates. Using a standard catalyst loading of 6 mol % often used in macrocyclization reactions, reactions were completed within 1 h in dichloromethane under static vacuum (30 mTorr) at 40° C. Twelve- to seventeen-membered rings were all synthesized with high Z-selectivity (95-99% Z) in moderate to high yields (68-79% isolated yield). Yuzu lactone, (Z)-Oxacyclotridec-10-en-2-one, for example, is in high demand by the perfume industry and can be synthesized more rapidly and selectively using ruthenium olefin metathesis catalysts than in previous reports. Larger macrocyclic lactones, fifteen-membered to seventeen-membered rings, were synthesized in slightly higher yields than with smaller twelve- to fourteen-membered.

In summary, highly active, ruthenium-based olefin metathesis catalysts were used for generating highly Z-macrocycles (95-99% Z) from easily available diene substrates with a Z-olefin moiety.

In another aspect, the macrocyclic musk compounds can be synthesized via ring closing olefin metathesis reactions of bis-olefins in the presence of at least one Group 8 metal olefin metathesis catalyst.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in a Z-configuration and is represented by the structure of Formula (A):

wherein: q is 1, 2, 3, or 4; and p is 4, 5, 6, or 7.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in a Z-configuration and is represented by the structure of Formula (B):

wherein: r is 1, 2, 3, or 4; and v is 4, 5, 6, or 7.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in a Z-configuration and is represented by the structure of Formula (C):

wherein: q^(c) is 1, 2, 3, or 4; and p^(c) is 4, 5, 6, or 7.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond and is represented by the structure of Formula (K):

wherein: x is 2, 3, 4 or 5; y is 5, 6, 7, or 8.

In another aspect the invention provides a method of forming a macrocyclic musk compound comprising the steps of cross metathesizing a first olefin and a second olefin in the presence of at least one Group 8 metal olefin metathesis catalyst, to form an intermediate of said first and second olefin and cyclizing the intermediate to form the macrocyclic musk compound.

These and other aspects of the present invention will be apparent to one of skill in the art, in light of the following detailed description and examples. Furthermore, it is to be understood that none of the embodiments or examples of the invention described herein are to be interpreted as being limiting.

DETAILED DESCRIPTION

Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an olefin” includes a single olefin as well as a combination or mixture of two or more olefins, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “for example”, “for instance”, “such as”, or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention and are not meant to be limiting in any fashion.

In this specification and in the claims, that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to 30 carbon atoms, generally containing 1 to 24 carbon atoms, typically 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” intends a cyclic alkyl group, typically having 3 to 12, or 4 to 12, or 3 to 10, or 3 to 8, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

The term “alkylene” as used herein refers to a divalent linear, branched, or cyclic alkyl group, where “alkyl” is as defined herein.

The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to 30 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Generally, “alkenyl” groups herein contain 2 to 24 carbon atoms, typically “alkenyl” groups herein contain 2 to 12 carbon atoms. The term “lower alkenyl” intends an “alkenyl” group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic “alkenyl” group, typically having 5 to 8 carbon atoms. The term “substituted alkenyl” refers to “alkenyl” substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to “alkenyl” in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing “alkenyl” and lower “alkenyl”, respectively. The term “alkenyl” is used interchangeably with the term “olefin” herein.

The term “alkenylene” as used herein refers to a divalent linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined herein.

The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to 30 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Generally, “alkynyl” groups herein contain 2 to 24 carbon atoms; typical “alkynyl” groups described herein contain 2 to 12 carbon atoms. The term “lower alkynyl” intends an “alkynyl” group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to “alkynyl” substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to “alkynyl” in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing “alkynyl” and lower “alkynyl” respectively.

The term “alkoxy” as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group can be represented as —O-alkyl where alkyl is as defined herein. A “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). “Aryl” groups contain 5 to 30 carbon atoms, generally “aryl” groups contain 5 to 20 carbon atoms; and typically, “aryl” groups contain 5 to 14 carbon atoms. Exemplary “aryl” groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups; for example, 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl, 2,6-di-iso-propylphenyl (i.e., DIPP or DiPP), 2-isopropyl-phenyl (i.e., IPP, Ipp or ipp), 2-iso-propyl-6-methylphenyl (i.e., MIPP or Mipp or MiPP). The terms “heteroatom-containing aryl” and “heteroaryl” refer to “aryl” substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined herein. An “aryloxy” group can be represented as —O-aryl where aryl is as defined herein. Preferred “aryloxy” groups contain 5 to 24 carbon atoms, and particularly preferred “aryloxy” groups contain 5 to 14 carbon atoms. Examples of “aryloxy” groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined herein. “Alkaryl” and “aralkyl” groups contain 6 to 30 carbon atoms; generally, “alkaryl” and “aralkyl” groups contain 6 to 20 carbon atoms; and typically, “alkaryl” and “aralkyl” groups contain 6 to 16 carbon atoms. “Alkaryl” groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of “aralkyl” groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula —OR wherein R is “alkaryl” or “aralkyl”, respectively, as defined herein.

The term “acyl” refers to substituents having the formula —(CO)-alkyl, —(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers to substituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or —O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as defined herein.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that can be monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and can be monocyclic, bicyclic, or polycyclic.

The terms “halo”, “halogen” and “halide” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

The term “hydrocarbyl” refers to univalent “hydrocarbyl” moieties containing 1 to 30 carbon atoms, typically containing 1 to 24 carbon atoms, specifically containing 1 to 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a “hydrocarbyl” group of 1 to 6 carbon atoms, typically 1 to 4 carbon atoms, and the term “hydrocarbylene” intends a divalent “hydrocarbyl” moiety containing 1 to 30 carbon atoms, typically 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term “lower hydrocarbylene” intends a “hydrocarbylene” group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to “hydrocarbyl” substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to “hydrocarbylene” substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and heterohydrocarbylene” refer to “hydrocarbylene” in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and/or heteroatom-containing “hydrocarbyl” and “hydrocarbylene” moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” can be monocyclic, bicyclic, or polycyclic as described herein with respect to the term “aryl.” Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—(CO)—X where X is halo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxyl (—COOH), carboxylato (—COO⁻), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato (—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino, di-(C₁-C₂₄ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino, di-(C₅-C₂₄ aryl)-substituted amino, (C₁-C₂₄ alkyl)(C₅-C₂₄ aryl)-substituted amino, (C₂-C₂₄ alkyl)-amido (—NH—(CO)-alkyl), (C₆-C₂₄ aryl)-amido (—NH—(CO)-aryl), imino (—CR═NH where R is hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), (C₂-C₂₀ alkyl)-imino (—CR═N(alkyl), where R is hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R is hydrogen, C₁-C₂ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato (—SO₂—O—), (C₁-C₂₄ alkyl)-sulfanyl (—S-alkyl; also termed “alkylthio”), (C₅-C₂₄ aryl)-sulfanyl (—S-aryl; also termed “arylthio”), (C₁-C₂₄ alkyl)-sulfinyl (—(SO)-alkyl), (C₅-C₂₄ aryl)-sulfinyl (—(SO)-aryl), (C₁-C₂₄ alkyl)-sulfonyl (—SO₂-alkyl), mono-(C₁-C₂₄ alkyl)-aminosulfonyl —SO₂—N(H)alkyl), di-(C₁-C₂₄ alkyl)-aminosulfonyl —SO₂—N(alkyl)₂, (C₅-C₂₄ aryl)-sulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino (—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂ alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂ alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferably C₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferably C₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl (preferably C₆-C₁₆ aralkyl).

The term “NHC” ligand, refers to a N-heterocyclic carbene ligand.

The term “CAAC” ligand, refers to a cyclic alkyl amino carbene ligand also known as “Bertrand-type ligand”.

Functional groups, such as ether, ester, hydroxyl, carbonate, may be protected in cases where the functional group interferes with the olefin metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 4rd Ed. (Published by John Wiley & Sons, Inc., Hoboken, N.J. 2007).

The geometry of the olefins described in this patent application may be of E-configuration, or of Z-configuration, or of a mixture of E- and Z-configurations. Applicants have represented a mixture of double-bond isomers by using a squiggly bond “

”. For example, as represented herein, structure

exemplifies either the E-configuration

or the Z-configuration

or can represent a mixture of E- and Z-configurations. Suitable ether protecting groups include a branched or non-branched alkyl moiety containing 1 to 5 carbon atoms, for example methyl, ethyl, propyl, i-propyl, t-Bu or t-amyl.

Suitable ester protecting groups include —C(O)R, wherein R=hydrogen, or a branched or non-branched alkyl moiety containing 1 to 7 carbon atoms, for example methyl, ethyl, propyl, i-propyl, t-butyl or t-amyl.

Suitable silyl ether protecting groups include —Si(R)₃; wherein R is a branched or unbranched alkyl moiety, which may include methyl, ethyl and propyl and t-butyl.

Suitable carbonate protecting groups include —C(O)OR, wherein R is a branched or non-branched alkyl moiety, for example methyl, ethyl or propyl.

By “sulfoxide group” is meant —[S(O)]—.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described herein. The term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

In addition, the functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated herein. Analogously, the herein-mentioned hydrocarbyl moieties can be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

“Optional” or “optionally” means that the subsequently described circumstance can or cannot occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent can or cannot be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Group 8 Metal Olefin Metathesis Catalyst

The Group 8 metal olefin metathesis catalysts of the invention are represented by the general structure of Formula (1)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group [—S(O)—];

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X¹ and X² are independently Cl, Br, I or F; and

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene.

In some embodiments of Formula (1),

wherein:

M, X¹ and X² are as defined herein;

X³ and X⁴ are independently O or S; and

R^(x), R^(y), R^(w) and R^(z) are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

The Group 8 metal olefin metathesis catalysts used in the invention can be represented by the structure of Formula (2):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ and L² are independently a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X³ and X⁴ are independently O or S; typically, X³ and X⁴ are independently S; and

R^(x), R^(y), R^(w) and R^(z) are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(x), R^(y), R^(w) and R^(z) are independently hydrogen, halogen, unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(x), R^(y), R^(w) and R^(z) are independently C₁-C₆ alkyl, hydrogen, unsubstituted phenyl, substituted phenyl or halogen; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

The Group 8 metal olefin metathesis catalysts used in the invention are represented by the structure of Formula (3),

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X¹ and X² are independently Cl, Br, I or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X⁵ and Y⁵ are independently C, CR^(3A), N, O, S, or P; only one of X⁵ or Y⁵ can be C or CR^(3A); typically, X⁵ and Y⁵ are independently N;

Q¹, Q², R³, R^(3A) and R⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q¹, Q², R³, R^(3A) and R⁴ are optionally linked to X⁵ or Y⁵ via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or —(CO)—; typically Q¹, Q², R³, R^(3A) and R⁴ are directly linked to X⁵ or Y⁵; and

p is 0 when X⁵ is O or S, p is 1 when X⁵ is N, P or CR^(3A), and p is 2 when X⁵ is C; q is 0 when Y⁵ is O or S, q is 1 when Y⁵ is N, P or CR^(3A), and q is 2 when X⁵ is C.

The Group 8 metal olefin metathesis catalysts used in the invention are represented by the structure of Formula (4):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

or R^(a) and R^(b) are linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X¹ and X² are independently Cl, Br, I or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X⁵ and Y⁵ are independently C, CR^(3A), or N; only one of X⁵ or Y5 can be C or CR^(3A); typically, X⁵ and Y⁵ are independently N;

R^(3A) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; Q is a linker, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; generally Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or —[CR¹¹═CR¹³]—; typically Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—, wherein R, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄ aryl;

“s” and “t” are independently 1 or 2; typically, “s” and “t” are independently 1; or any two of R, R¹², R¹³, and R¹⁴ are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R⁴ is, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl or 2-methyl-phenyl; or when X⁵ is CR^(3A), then R^(3A) and R⁴ can from together a five to ten membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached.

In some embodiments of Formula (4),

wherein: X¹, X², X³, X⁴, M, R^(x), R^(y), R^(w) and R^(z) are as defined herein.

When Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t), s is 1, t is 1 and R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, and M is ruthenium, then olefin metathesis catalyst of Formula (4), is represented by the structure of Formula (5)

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted hetero atom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; typically, R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally, X¹ and X² are independently Cl, Br, I or F; typically, X¹ and X² are independently Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (5) are described in Table (1), wherein X¹ is Cl and X² is Cl.

TABLE (1) Olefin Metathesis Catalysts of Formula (5) Catalyst R¹ R² R³ R⁴ R^(a) R^(b) 1 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 2 H Ph Mes Mes Me Me 3 H Ph Mipp Mipp Me Me 4 H Ph adamantyl Mes Me Me 5 H Ph DIPP DIPP Me Me 6 H Ph IPP IPP Me Me 7 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 8 H

Mes Mes Me Me 9 H

Mipp Mipp Me Me 10 H

adamantyl Mes Me Me 11 H

DIPP DIPP Me Me 12 H

IPP IPP Me Me 13 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 14 H

Mes Mes Me Me 15 H

Mipp Mipp Me Me 16 H

adamantyl Me Me Me 17 H

DIPP DIPP Me Me 18 H

IPP IPP Me Me 19

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 20

Mes Mes Me Me 21

Mipp Mipp Me Me 22

adamantyl Mes Me Me 23

DIPP DIPP Me Me 24

IPP IPP Me Me 25 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

26 H Ph Mes Mes

27 H Ph Mipp Mipp

28 H Ph adamantyl Mes

29 H Ph DIPP DIPP

30 H Ph IPP IPP

31 H

2-Me—C₆H₅ 2-Me—C₆H₅

32 H

Mes Mes

33 H

Mipp Mipp

34 H

adamantyl Mes

35 H

DIPP DIPP

36 H

IPP IPP

37 H

2-Me—C₆H₅ 2-Me—C₆H₅

38 H

Mes Mes

39 H

Mipp Mipp

40 H

adamantyl Mes

41 H

DIPP DIPP

42 H

IPP IPP

43

2-Me—C₆H₅ 2-Me—C₆H

44

Mes Mes

45

Mipp Mipp

46

adamantyl Mes

47

DIPP DIPP

48

IPP IPP

49 H Ph 2-Me—C₆H 2-Me—C₆H n-Bu n-Bu 50 H Ph Mes Mes n-Bu n-Bu 51 H Ph Mipp Mipp n-Bu n-Bu 52 H Ph adamantyl Mes n-Bu n-Bu 53 H Ph DIPP DIPP n-Bu n-Bu 54 H Ph IPP IPP n-Bu n-Bu 55 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 56 H

Mes Mes n-Bu n-Bu 57 H

Mipp Mipp n-Bu n-Bu 58 H

adamantyl Mes n-Bu n-Bu 59 H

DIPP DIPP n-Bu n-Bu 60 H

IPP IPP n-Bu n-Bu 61 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 62 H

Mes Mes n-Bu n-Bu 63 H

Mipp Mipp n-Bu n-Bu 64 H

adamantyl Mes n-Bu n-Bu 65 H

DIPP DIPP n-Bu n-Bu 66 H

IPP IPP n-Bu n-Bu 67

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 68

Mes Mes n-Bu n-Bu 69

Mipp Mipp n-Bu n-Bu 70

adamantyl Mes n-Bu n-Bu 71

DIPP DIPP n-Bu n-Bu 72

IPP IPP n-Bu n-Bu wherein: Mes is

Mipp is

DIPP is

adamantyl is

IPP is

2-Me-C₆H₅ is

Me is CH₃—, n-Bu is [CH₃—(CH₂)₃—], Ph is

and

is [—(CH₂)₄—].

When Q is a two-atom linkage having the structure —[CR¹¹═CR¹³]— and R¹¹ and R¹³ are hydrogen, and M is ruthenium, then the olefin metathesis catalyst of Formula (4), is represented by the structure of Formula (6)

wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; or R^(a) and R^(b) are linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; X¹ and X² are independently Cl, Br, I or F; typically, X¹ and X² are independently Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₁-C₁₀ cycloalkyl, substituted C₁-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (6) are described in Table (2), wherein X¹ is Cl and X² is Cl.

TABLE (2) Olefin Metathesis Catalysts of Formula (6) Catalyst R¹ R² R³ R⁴ R^(a) R^(b) 73 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 74 H Ph Mes Mes Me Me 75 H Ph Mipp Mipp Me Me 76 H Ph adamantyl Mes Me Me 77 H Ph DIPP DIPP Me Me 78 H Ph IPP IPP Me Me 79 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 80 H

Mes Mes Me Me 81 H

Mipp Mipp Me Me 82 H

adamantyl Mes Me Me 83 H

DIPP DIPP Me Me 84 H

IPP IPP Me Me 85 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 86 H

Mes Mes Me Me 87 H

Mipp Mipp Me Me 88 H

adamantyl Mes Me Me 89 H

DIPP DIPP Me Me 90 H

IPP IPP Me Me 91

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 92

Mes Mes Me Me 93

Mipp Mipp Me Me 94

adamantyl Mes Me Me 95

DIPP DIPP Me Me 96

IPP IPP Me Me 97 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

98 H Ph Mes Mes

99 H Ph Mipp Mipp

100 H Ph adamantyl Mes

101 H Ph DIPP DIPP

102 H Ph IPP IPP

103 H

2-Me—C₆H₅ 2-Me—C₆H₅

104 H

Mes Mes

105 H

Mipp Mipp

106 H

adamantyl Mes

107 H

DIPP DIPP

108 H

IPP IPP

109 H

2-Me—C₆H₅ 2-Me—C₆H₅

110 H

Mes Mes

111 H

Mipp Mipp

112 H

adamantyl Mes

113 H

DIPP DIPP

114 H

IPP IPP

115

2-Me—C₆H₅ 2-Me—C₆H₅

116

Mes Mes

117

Mipp Mipp

118

adamantyl Mes

119

DIPP DIPP

120

IPP IPP

121 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 122 H Ph Mes Mes n-Bu n-Bu 123 H Ph Mipp Mipp n-Bu n-Bu 124 H Ph adamantyl Mes n-Bu n-Bu 125 H Ph DIPP DIPP n-Bu n-Bu 126 H Ph IPP IPP n-Bu n-Bu 127 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 128 H

Mes Mes n-Bu n-Bu 129 H

Mipp Mipp n-Bu n-Bu 130 H

adamantyl Mes n-Bu n-Bu 131 H

DIPP DIPP n-Bu n-Bu 132 H

IPP IPP n-Bu n-Bu 133 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 134 H

Mes Mes n-Bu n-Bu 135 H

Mipp Mipp n-Bu n-Bu 136 H

adamantyl Mes n-Bu n-Bu 137 H

DIPP DIPP n-Bu n-Bu 138 H

IPP IPP n-Bu n-Bu 139

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 140

Mes Mes n-Bu n-Bu 141

Mipp Mipp n-Bu n-Bu 142

adamantyl Mes n-Bu n-Bu 143

DIPP DIPP n-Bu n-Bu 144

IPP IPP n-Bu n-Bu

When, Y is N and X⁵ is CR^(3A) and M is ruthenium then, the olefin metathesis catalyst of Formula (4), is represented by the structure of Formula (7)

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁ alkyl, unsubstituted C₃-C₁ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; generally, X¹ and X² are independently Cl, Br, I or F; typically, X¹ and X² are independently Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl or 2-methyl-phenyl;

R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl or substituted C₆-C₂₄ heteroaralkyl; typically, R¹¹ and R¹² are independently methyl and R¹³ and R¹⁴ are independently hydrogen;

R^(3A) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(3A) is unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl or substituted C₆-C₂₄ heteroaralkyl; typically R^(3A) is methyl, ethyl, n-propyl, or phenyl; or R^(3A) together with R⁴ can form a five to ten membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached; and

R⁴ is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl or substituted C₆-C₂₄ heteroaralkyl; typically R⁴ is methyl, ethyl, n-propyl, or phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (7) are described in Table (3), wherein X¹ is Cl, X² is Cl, R¹¹ is methyl, R¹² is methyl, R¹³ is hydrogen and R¹⁴ is hydrogen.

TABLE (3) Olefin Metathesis Catalysts of Formula (7) Catalyst R¹ R² R^(a) R^(b) R³ R^(3A) R⁴ 145 H Ph Me Me 2-Me—C₆H₅ Me Me 146 H Ph Me Me Mes Me Me 147 H Ph Me Me Mipp Me Me 148 H Ph Me Me EMP Me Me 149 H Ph Me Me DIPP Me Me 150 H Ph Me Me IPP Me Me 151 H

Me Me 2-Me—C₆H₅ Me Me 152 H

Me Me Mes Me Me 153 H

Me Me Mipp Me Me 154 H

Me Me EMP Me Me 155 H

Me Me DIPP Me Me 156 H

Me Me IPP Me Me 157 H

Me Me 2-Me—C₆H₅ Me Me 158 H

Me Me Mes Me Me 159 H

Me Me Mipp Me Me 160 H

Me Me EMP Me Me 161 H

Me Me DIPP Me Me 162 H

Me Me IPP Me Me 163

Me Me 2-Me—C₆H₅ Me Me 164

Me Me Mes Me Me 165

Me Me Mipp Me Me 166

Me Me EMP Me Me 167

Me Me DIPP Me Me 168

Me Me IPP Me Me 169 H Ph

2-Me—C₆H₅ Me Me 170 H Ph

Mes Me Me 171 H Ph

Mipp Me Me 172 H Ph

EMP Me Me 173 H Ph

DIPP Me Me 174 H Ph

IPP Me Me 175 H

2-Me—C₆H₅ Me Me 176 H

Mes Me Me 177 H

Mipp Me Me 178 H

EMP Me Me 179 H

DIPP Me Me 180 H

IPP Me Me 181 H

2-Me—C₆H₅ Me Me 182 H

Mes Me Me 183 H

Mipp Me Me 184 H

EMP Me Me 185 H

DIPP Me Me 186 H

IPP Me Me 187

2-Me—C6H5 Me Me 188

Mes Me Me 189

Mipp Me Me 190

EMP Me Me 191

DIPP Me Me 192

IPP Me Me 193 H Ph n-Bu n-Bu 2-Me—C₆H₅ Me Me 194 H Ph n-Bu n-Bu Mes Me Me 195 H Ph n-Bu n-Bu Mipp Me Me 196 H Ph n-Bu n-Bu EMP Me Me 197 H Ph n-Bu n-Bu DIPP Me Me 198 H Ph n-Bu n-Bu IPP Me Me 199 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 200 H

n-Bu n-Bu Mes Me Me 201 H

n-Bu n-Bu Mipp Me Me 202 H

n-Bu n-Bu EMP Me Me 203 H

n-Bu n-Bu DIPP Me Me 204 H

n-Bu n-Bu IPP Me Me 205 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 206 H

n-Bu n-Bu Mes Me Me 207 H

n-Bu n-Bu Mipp Me Me 208 H

n-Bu n-Bu EMP Me Me 209 H

n-Bu n-Bu DIPP Me Me 210 H

n-Bu n-Bu IPP Me Me 211

n-Bu n-Bu 2-Me—C₆H₅ Me Me 212

n-Bu n-Bu Mes Me Me 213

n-Bu n-Bu Mipp Me Me 214

n-Bu n-Bu EMP Me Me 215

n-Bu n-Bu DIPP Me Me 216

n-Bu n-Bu IPP Me Me wherein EMP is

When, L¹ is a CAAC ligand of formula:

m is 0, and M is ruthenium then, the olefin metathesis catalyst of Formula (1), is represented by the structure of Formula (7A)

wherein X¹, X², R¹, R², R^(a) and R^(b) are as defined herein;

X is —CR^(1a)R^(2a)—;

a is 1 or 2;

R^(1a) is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl, optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀ heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)XR²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with R^(2a) forms an optionally substituted spiro monocyclic or spiro polycyclic C₃₋₁₀cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R³ or together with R⁴ forms an optionally substituted polycyclic ring;

R^(2a) is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl, optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀ heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with Ria forms a spiro monocyclic or spiro polycyclic C₃₋₁₀cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R³ or together with R⁴ forms an optionally substituted polycyclic ring;

Y is —CR^(1b)R^(2b)—;

b is 0, 1 or 2;

R^(1b) is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl, optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀ heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with R^(2b) forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;

R^(2b) is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, halogen, optionally substituted C₅-C₂₄ aryl, optionally substituted C₆-C₂₄ aralkyl, optionally substituted C₁-C₂₀ heteroalkyl, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)XR²⁵, P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, or together with R^(1b) forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;

R^(3a) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴ NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R^(1a) or together with R^(2a) can form an optionally substituted polycyclic ring, or together with R^(3a) can form an optionally substituted spiro monocyclic or spiro polycyclic C₃₋₁₀ cycloalkyl;

R^(3b) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R^(1a) or together with R^(2a) can form an optionally substituted polycyclic ring, or together with R³ can form an optionally substituted spiro monocyclic or spiro polycyclic C₃₋₁₀ cycloalkyl;

R^(4a) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with Ria or together with R^(2a) can form an optionally substituted polycyclic ring, or together with R^(4a) can form an optionally substituted spiro monocyclic or spiro polycyclic C₃₋₁₀ cycloalkyl;

R^(4b) is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R^(1a) or together with R^(2a) can form an optionally substituted polycyclic ring, or together with R⁴ can form an optionally substituted spiro monocyclic or spiro polycyclic C₃₋₁₀ cycloalkyl;

R⁵ is H, optionally substituted C₁₋₂₄ alkyl, halogen-C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R², —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R⁶ can form an optionally substituted polycyclic ring;

R⁶ is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl or together with R⁵ or together with R⁷ can form an optionally substituted polycyclic ring;

R⁷ is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R⁶ or together with R⁸ can form an optionally substituted polycyclic ring;

R⁸ is H, optionally substituted C₁₋₂₄ alkyl, halogen-C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R⁷ or together with R⁹ can form an optionally substituted polycyclic ring;

R⁹ is H, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²¹, —OR²², CN, —NR²³R²⁴, NO₂, —CF₃, —S(O)_(x)R²⁵, —P(O)(OH)₂, —OP(O)(OH)₂, —SR²⁷, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substituted C₃₋₈ cycloalkenyl, or together with R⁸ can form a polycyclic ring;

R²¹ is OH, OR²⁶, NR²³R²⁴, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²² is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²³ is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²⁴ is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²⁵ is H, optionally substituted C₁₋₂₄ alkyl, OR²², —NR²³R²⁴, optionally substituted heterocycle, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R²⁶ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

R² is H, optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₁₀ cycloalkyl, optionally substituted heterocycle, optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;

x is 1 or 2; and with the provisos

a. when a is 2, then the “X-X” bond can be saturated or unsaturated;

b. when b is 2, the “Y-Y” bond can be saturated or unsaturated;

c. when a is 2, and the “X-X” bond is unsaturated, then R^(2a) is nil;

d. when b is 1, then R^(3a) and R^(4a) are both nil;

e. when b is 2, then R^(3a) and R^(4a) are both nil; and

f. when b is 2, and the “Y-Y” bond is unsaturated, then R^(2b) is nil.

Depending on the values of a, b, X and Y, Moiety (A) of the CAAC ligand

is represented by structures selected from Table (4).

TABLE (4) Structures of Moiety (A) of the CAAC ligands

(A1)

(A2)

(A3)

(A4)

(A5)

(A6)

(A7)

(A8)

(A9)

(A10)

(A11)

(A12)

(A13) wherein: R¹, R², R^(a), R^(b), R^(3a), R^(3b), R^(4a), R^(4b), R⁵, R⁶, R⁷, R⁸ R⁹, R^(1a), R^(1b), X¹, X², X, and Y are as defined herein.

The nomenclature of the structures of Formula (7A) is determined by the Moiety (A) structures selected from Table (4). For example, the structure below is assigned Formula (7A2), since Moiety (A2) is present in the CAAC ligand.

TABLE (5) Olefin Metathesis Catalysts of Formula (7A)

Formula (7A10)

Formula (7A13)

Formula (7A12)

Formula (7A6)

Formula (7A11)

Formula (7A8)

Formula (7A9)

Formula (7A7)

Formula (7A5)

Formula (7A4)

Formula (7A3)

Formula (7A1) wherein: R¹, R², R^(a), R^(b) R^(3a), R^(3b), R^(4a), R^(4b), R⁵, R⁶, R⁷, R⁸ R⁹, R^(1a), R^(1b), X¹, X², X, and Y are as defined herein.

When, L¹ is a N-heterocyclic carbene ligand represented by

and X³ and X⁴ are independently S, and M is ruthenium then, the olefin metathesis catalyst of Formula (2), is represented by the structure of Formula (8)

wherein:

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group;

R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl;

R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl, or hydrogen; generally, R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen; and

R^(x), R^(y), R^(w) and R^(z) are independently C₁-C₆ alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; generally R^(x) is methyl, hydrogen or Cl, R^(y) is hydrogen, R^(w) is hydrogen, R^(z) is Cl, t-butyl, hydrogen or phenyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (8) are described in Table (6), wherein R^(a) is methyl, R^(b) is methyl, R¹¹ is hydrogen, R¹² is hydrogen, R¹³ is hydrogen, R¹⁴ is hydrogen, R^(y) is hydrogen and R^(w) is hydrogen.

TABLE (6) Olefin Metathesis Catalysts of Formula (8) Cata- lyst R¹ R² R³ R⁴ R^(x) R^(z) 217 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 218 H Ph Mes Mes Cl Cl 219 H Ph Mipp Mipp Cl Cl 220 H Ph DIPP DIPP Cl Cl 221 H Ph IPP IPP Cl Cl 222 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 223 H

Mes Mes Cl Cl 224 H

Mipp Mipp Cl Cl 225 H

DIPP DIPP Cl Cl 226 H

IPP IPP Cl Cl 227 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 228 H

Mes Mes Cl Cl 229 H

Mipp Mipp Cl Cl 230 H

DIPP DIPP Cl Cl 231 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 232 H

Mes Mes Cl Cl 233 H

Mipp Mipp Cl Cl 234 H

DIPP DIPP Cl Cl 235 H

IPP IPP Cl Cl 236 H

IPP IPP Cl Cl 237

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 238

Mes Mes Cl Cl 239

Mipp Me Cl Cl 240

DIPP DIPP Cl Cl 241

IPP Me Cl Cl 242 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 243 H Ph Mes Mes H Ph 244 H Ph Mipp Mipp H Ph 245 H Ph DIPP DIPP H Ph 246 H Ph IPP IPP H Ph 247 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 248 H

Mes Mes H Ph 249 H

Mipp Mipp H Ph 250 H

DIPP DIPP H Ph 251 H

IPP IPP H Ph 252 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 253 H

Mes Mes H Ph 254 H

Mipp Mipp H Ph 255 H

DIPP DIPP H Ph 256 H

IPP IPP H Ph 257

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 258

Mes Mes H Ph 259

Mipp Mipp H Ph 260

DIPP DIPP H Ph 261

IPP IPP H Ph 262 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 263 H Ph Mes Mes Me t-Bu 264 H Ph Mipp Mipp Me t-Bu 265 H Ph DIPP DIPP Me t-Bu 266 H Ph IPP IPP Me t-Bu 267 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 268 H

Mes Mes Me t-Bu 269 H

Mipp Mipp Me t-Bu 270 H

DIPP DIPP Me t-Bu 271 H

IPP IPP Me t-Bu 272 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 273 H

Mes Mes Me t-Bu 274 H

Mipp Mipp Me t-Bu 275 H

DIPP DIPP Me t-Bu 276 H

IPP IPP Me t-Bu 277

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 278

Mes Mes Me t-Bu 279

Mipp Mipp Me t-Bu 280

DIPP DIPP Me t-Bu 281

IPP IPP Me t-Bu

Non-limiting examples of catalysts used in the present invention are represented by the structures:

When L¹ is a CAAC ligand and

and, X³ and X⁴ are independently S, and M is ruthenium then, the olefin metathesis catalyst of Formula (2), is represented by the structure of Formula (8A)

wherein: R¹, R², R^(a), R^(b) R^(3a), R^(3b), R^(4a), R^(4b) R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(z), R^(w), X, Y, a and b are as defined herein.

The nomenclature of the structures of Formula (8A) is determined by the Moiety (A) structures selected from Table (4). For example, the structure below is assigned Formula (8A10), since Moiety (A10) is present in the CAAC ligand.

TABLE (7) Olefin Metathesis Catalysts of Formula (8A)

Formula (8A5)

Formula (8A4)

Formula (8A1)

Formula (8A11)

Formula (8A2)

Formula (8A3)

Formula (8A8)

Formula (8A13)

Formula (8A12)

Formula (8A6)

Formula (8A7)

Formula (8A9) wherein: R¹, R^(1a), R^(1b), R², R^(a), R^(b) R^(3a), R^(3b), R^(4a), R^(4b) R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(z), R^(w), X, Y, a and b are as defined herein.

In other embodiments of the invention, the Group 8 metal olefin metathesis catalysts of the invention are represented by the general structure of Formula (9)

wherein: M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; generally, m is 0 or 1; typically, m is 0;

R^(aa) is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(aa) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(aa) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(bb) is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(b)b is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(b)b is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(aa) and R^(b)b can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atom they are linked to;

R^(cc) is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(cc) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(dd) is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally R^(d) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically R^(d)d is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^(cc) and R^(dd) can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atom they are linked to;

R^(bb) and R^(cc) can be linked to form a five-, six- or seven-membered heterocycle ring with the nitrogen atoms they are linked to;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; typically, X¹ and X² are independently chlorine, bromine, iodine or fluorine;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene.

In some embodiments of Formula (9),

is represented by

wherein: M, X¹, X², X³, X⁴, R^(x), R^(y), R^(w) and R^(z) are as defined herein.

In some embodiments of Formula (9), L¹ is

represented by

or by or L¹ is a CAAC ligand represented by

wherein Q¹, Q², p, q, R^(3a), R^(3b) R^(4a), R^(4b), R³, R⁴, R⁵ R⁶, R⁷, R⁸, R⁹, X⁵, Y⁵, a and b are as defined herein.

When M is Ru, n is 0, m is 0 and L¹ is a NHC ligand of structures

then the invention provides a catalyst represented by structures

and when

is represented by

then the invention provides a catalyst represented by structures

wherein R, R², R³, R⁴, R^(aa), R^(bb) R^(cc), R^(dd), X¹, X², X³, X⁴, R¹¹, R¹², R¹³, R¹⁴, R^(x), R^(y), R^(w) and R^(z) are as defined herein.

When M is Ru, n is 0, m is 0 and L is a CAAC ligand then the invention provides a catalyst represented by the structure of Formula (10A)

wherein: R¹, R², X¹, X², R^(3a), R^(3b), R^(4a), R^(4b), R^(aa), R^(bb), R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, X, Y, a and b are as defined herein.

The nomenclature of the structures of Formula (10A) is determined by the Moiety (A) structures selected from Table (4). For example, the structure below is assigned Formula (10A10), since Moiety (A10) is present in the CAAC ligand.

TABLE (8) Olefin Metathesis Catalysts of Formula (10A)

Formula (10A5)

Formula (10A4)

Formula (10A1)

Formula (10A11)

Formula (10A2)

Formula (10A3)

Formula (10A8)

Formula (10A13)

Formula (10A12)

Formula (10A6)

Formula (10A7)

Formula (10A9) wherein: R¹, R^(1a), R^(1b), R², R^(a), R^(b) R^(3a), R^(3b), R^(4a), R^(4b), R^(aa), R^(bb), R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(z) R^(w), X, Y, a and b are as defined herein.

When M is Ru, n is 0, m is 0,

is represented by

X³ and X⁴ are S, and L¹ is a CAAC ligand then the invention provides a catalyst represented by the structure of Formula (12A)

wherein: R¹, R², R^(3a), R^(3b), R^(4a), R^(4b), R^(aa), R^(bb), R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(w), R^(z), X, Y, a and b are as defined herein.

The nomenclature of the structures of Formula (12A) is determined by the Moiety (A) structures selected from Table (4). For example, the structure below is assigned Formula (12A5), since Moiety (A5) is present in the CAAC ligand.

TABLE (9) Olefin Metathesis Catalysts of Formula (12A)

Formula (12A0)

Formula (12A4)

Formula (12A1)

Formula (12A11)

Formula (12A2)

Formula (12A3)

Formula (12A8)

Formula (12A13)

Formula (12A12)

Formula (12A6)

Formula (12A7)

Formula (12A9) wherein: R¹, R², R^(1a), R^(1b), R^(3a), R^(3b), R^(4a), R^(4b), R^(aa), R^(bb), R^(cc), R^(dd), R⁵, R⁶, R⁷, R⁸ R⁹, R^(x), R^(y), R^(w), R^(z), X, Y, a and b are as defined herein.

Non-limiting examples of catalysts used in the present invention are represented by the structures:

Description of the Macrocyclic Embodiments

In one embodiment, the ring-close metathesis macrocyclic product comprises a product internal olefin, wherein the product internal olefin is in a Z-configuration.

In some embodiments, the invention provides a method that produces a compound (i.e., a product, olefin product; e.g., ring-close metathesis product) having a carbon-carbon double bond (e.g., a product internal olefin) in a Z:E ratio greater than 95:5, greater than 96:4, greater than 97:3, greater than 98:2, or in some cases, greater than 99:1. In some cases, about 100% of the carbon-carbon double bond produced in the metathesis reaction may have a Z configuration. The Z or cis selectivity may also be expressed as a percentage of product formed (e.g., ring-close metathesis product). In some cases, the product (e.g., ring-close metathesis product) may be greater than 50% Z, greater than 60% Z, greater than 70% Z, greater than 80% Z, greater than 90% Z, greater than 95% Z, greater than 96% Z, greater than 97% Z, greater than about 98% Z, greater than 99% Z, or in some cases greater than 99.5% Z.

In one embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in a Z configuration and is represented by the structure of Formula (A):

wherein: q is 1, 2, 3, or 4; and p is 4, 5, 6, or 7.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (A), wherein q is 2 and p is 4 or 6.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (A), wherein q is 1, 2, 3 or 4 and p is 6 or 7.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (A), wherein, q is 1 or 2 and p is 6.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (A), wherein q is 1, 2, 3 or 4 and p is 7.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (A), wherein, q is 1 and p is 6.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in a Z configuration and is represented by the structure of Formula (B):

wherein: r is 1, 2, 3, or 4; and v is 4, 5, 6, or 7.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (B), wherein r is 2 and v is 4 or 6.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (B), wherein r is 1, 2, 3 or 4 and v is 6 or 7.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (B), wherein, r is 1 or 2 and v is 6.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (B), wherein r is 1, 2, 3 or 4 and v is 7.

In another embodiment, the at least one ring-close metathesis product is represented by the structure of Formula (B), wherein, r is 1 and v is 6.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (E):

wherein: R^(e) is H, methyl, ethyl, or propyl; q is 1, 2, 3, or 4; p is 4, 5, 6, or 7.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (E), wherein R^(e) is methyl, q is 2 and p is 4 or 6.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (E), wherein R^(e) is ethyl, q is 1, 2, 3 or 4 and p is 6 or 7.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (E), wherein R^(e) is ethyl, q is 1 or 2 and p is 6.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (E), wherein R^(e) is ethyl, q is 1, 2, 3 or 4 and p is 7.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (E), wherein R^(e) is ethyl, q is 1 and p is 6.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one olefin metathesis catalyst of Formula (5), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one olefin metathesis catalyst of Formula (6), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one olefin metathesis catalyst of Formula (7), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (8), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (8A), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (9), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (10), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (10A), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (11), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (12), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In another embodiment, the invention relates to a method for performing a ring-closing metathesis reaction, comprising: contacting a diene starting material bearing a Z-olefin moiety of Formula (E), with at least one Z-stereoretentive olefin metathesis catalyst of Formula (12A), under conditions effective to promote the formation of at least one Z-macrocycle product of Formula (A), with a Z-configuration greater than 80% Z.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle, represented by Formula (A), comprising, a ring closing metathesis reaction on a diene of Formula (E), in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (5), and wherein R^(e), q, p, R¹, R², R^(a), R^(b), X¹, X², R³ and R⁴ are as defined herein.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle, represented by Formula (A), comprising, a ring closing metathesis reaction on a diene of Formula (E), in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (8), and wherein R^(e), q, p, R¹, R², R^(a), R^(b), R¹¹, R¹², R¹³, R¹⁴, R³, R⁴, R^(x), R^(y), R^(z) and R^(w) are as defined herein.

In one embodiment a Z-olefin moiety represented by Formula (E), wherein R^(e) is methyl, q is 2 and p is 4 or 6; is reacted in the presence of a catalyst represented by of Formula (8), wherein R¹ is hydrogen, R² is phenyl, ethyl or together with R¹ can form a phenylindenylidene, R^(a) is methyl, R^(b) is methyl, R¹¹ is hydrogen, R¹² is hydrogen, R¹³ is hydrogen, R¹⁴ is hydrogen, R³ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl, R^(x) is Cl, R^(y) is hydrogen, R^(z) is Cl and R^(w) is hydrogen, to give a musk macrocycle of Formula (A) with a Z-configuration greater than 80% Z.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle of Formula (A) comprising, performing a ring closing metathesis reaction on a diene of Formula (E) wherein R^(e) is H, methyl, ethyl, or propyl; q is 1, 2, 3, or 4; p is 4, 5, 6, or 7; in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (5), wherein the catalyst is selected from: C591, C731, C625, C763, C663, C641, C647m, C747, C647, C676, C773, C673, C651 and C831m.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle of Formula (A) comprising, performing a ring closing metathesis reaction on a diene of Formula (E) wherein R^(e) is H, methyl, ethyl, or propyl; q is 1, 2, 3, or 4; p is 4, 5, 6, or 7; in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (8), wherein the catalyst is selected from: C885ss, C785ss, C738ss, C869ss, and C725ss.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle of Formula (B) comprising, performing a ring closing metathesis reaction on a diene of Formula (E) wherein R^(e) is H, methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7; in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (12), wherein the catalyst is selected from: C801_(TU), C701_(TU), C885_(TU), C881_(TU), C799_(TU), C951_(TU) and C799u_(TU).

In one embodiment, the invention provides for a method of synthesizing dilactones, such as ethylene brassylate (x=9) and ethylene undecanedioate (x=7), both used in perfumery, wherein the starting material can be obtained from a cross metathesis reaction in the presence of at least one metal olefin metathesis catalyst of the invention. The olefin is further reduced and cyclized using known procedures.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (F):

wherein: R^(f) is H, methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (F), wherein R^(f) is methyl, r is 2 and v is 4 or 6.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (F), wherein R^(f) is ethyl, r is 1, 2, 3 or 4 and v is 6 or 7.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (F), wherein R^(f) is ethyl, r is 1 or 2 and v is 6.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (F), wherein R^(f) is ethyl, r is 1, 2, 3 or 4 and v is 7.

In one embodiment, the diene starting material bearing a Z-olefin moiety can be represented by Formula (F), wherein R^(f) is ethyl, r is 1 and v is 6.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle of Formula (B) comprising, performing a ring closing metathesis reaction on a diene of Formula (F) wherein R^(f) is H, methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7; in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (5), wherein the catalyst is selected from: C591, C731, C625, C763, C663, C641, C647m, C747, C647, C676, C773, C673, C651 and C831m.

In one embodiment, the invention provides for a method of synthesizing a musk macrocycle of Formula (B) comprising, performing a ring closing metathesis reaction on a diene of Formula (F) wherein R^(f) is H, methyl, ethyl, or propyl; r is 1, 2, 3, or 4; v is 4, 5, 6, or 7; in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (8), wherein the catalyst is selected from: C885ss, C785ss, C738ss, C869ss, and C725ss.

In one embodiment the invention, provides for a method for synthesizing a musk macrocycle, represented by Formula (K)

the method comprising: a) contacting an olefin represented by Formula (G)

with at least one metathesis reaction partner represented by Formula (H)

in the presence of at least one olefin metathesis catalyst of Formula (4), Formula (5), Formula (6), or Formula (7), under conditions sufficient to form a metathesis product represented by the structure of Formula (J):

wherein R^(1m) is H or methyl; OR^(2m) is a protected hydroxyl group, which may be selected from an alkyl ether group; an ester group; a silyl ether group; or a carbonate group; R^(3m) is branched or straight C₁-C₅ alkyl; x is 2, 3, 4 or 5; and y is 5, 6, 7, or 8.

In one embodiment the invention, provides for a method for synthesizing a musk macrocycle, represented by Formula (K)

the method comprising: a) contacting an olefin represented by Formula (G)

with at least one metathesis reaction partner represented by Formula (H)

in the presence of at least one olefin metathesis catalyst of Formula (8), Formula (8A), Formula (9), Formula (10), Formula (10A), Formula (11), Formula (12), Formula (12A) or Formula (13) under conditions sufficient to form a metathesis product represented by the structure of Formula (J):

wherein R^(1m) is H or methyl; OR^(2m) is a protected hydroxyl group, which may be selected from an alkyl ether group; an ester group; a silyl ether group; or a carbonate group; R^(3m) is branched or straight C₁-C₅ alkyl; x is 2, 3, 4 or 5; and y is 5, 6, 7, or 8.

In one embodiment of the invention, one or both of first and second olefins may be olefins with a terminal double bond.

In one embodiment of the invention one of the first or second olefin may be represented by the Formula (G), wherein: R^(1m) is H or methyl; OR^(2m) is a protected hydroxyl group, which may be selected from an alkyl ether group; an ester group; a silyl ether group; or a carbonate group; and x is 2, 3, 4 or 5.

In one embodiment of the invention one of the first or second olefin may be represented by the Formula (H), wherein: R^(3m) is branched or straight C₁-C₅ alkyl; and y is 5, 6, 7, or 8.

In one embodiment of the invention, the intermediate formed during the cross-metathesis reaction between the first olefin of Formula (G), and the second olefin, of Formula (H), in the presence of at least one ruthenium olefin metathesis catalyst, can be represented by the Formula (J), wherein: R^(1m) is H or methyl; OR^(2m) is a protected hydroxyl group, which may be selected from an alkyl ether group, an ester group, a silyl ether group and a carbonate group; R^(3m) is branched or straight C₁-C₅ alkyl; x is 2, 3, 4 or 5; R^(3m) is branched or straight C₁-C₅ alkyl; and y is 5, 6, 7, or 8.

TABLE (10) Musk Macrocycles name y x E/Z ambrettolide 7 6 7-ambrettolide 5 8 habanolide 9 3 9-hexadecen-16-olide 7 5

The intermediate of Formula (J) can be formed in the presence of any of the ruthenium metathesis catalysts represented by Formula (1), Formula (2), Formula (3), Formula (4), Formula (5), Formula (6), Formula (7), Formula (8), Formula (8A), Formula (9), Formula (10), Formula (10A), Formula (11), Formula (12), Formula (12A) or Formula (13). The ruthenium catalyst can be selected from any of the structures defined, represented or exemplified herein.

Macrocyclic Products

Common macrocyclic musk compounds include ambrettolide (9-ambrettolide and 7-ambrettolide), nirvanolide, habanolide, cosmone, muscenone, velvione, civetone and globanone.

For example, the first and second olefin compounds that can be used to form 7-ambrettolide may be selected from 10-(tert-butoxy)dec-1-ene and methyl oct-7-enoate or dec-9-en-1-yl acetate and methyl oct-7-enoate. The first and second olefin compounds that can be used to form Habanolide may be selected from trimethyl (pent-4-en-1-yloxy)silane and ethyl dodec-11-enoate. The first and second olefin compounds that can be used to form Nirvanolide may be selected from 4-methyl-6-(tert-butoxy)hex-1-ene and methyl 9-decenoate, or 4-methy 1-6-(tert-butoxy)hex-1-ene and ethyl-9-decenoate, or 3-methylhex-5-en-1-ylpropionate and methyl 9-decenoate.

As such, the method of the present invention, whereby a hetero-dimer is first formed by metathesis, and then ring-closed by a macrocyclization step, represents a considerably simpler and cheaper process than RCM to form macrocyclic musk compounds, which is industrially scalable in an economic manner.

As described above, a number of the macrocyclic derivatives obtained via the methods of the invention can be used in the fragrance and flavor industry. The macrocyclic derivatives include, for example, the compounds listed in Table (11).

TABLE (11) Macrocyclic Products Name Structure (R)-(+)- Muscopyridine

(R)-(−)-Muscone

(Z)-oxacyclododec-8- en-2-one

Ethylene undecanedioate

Civetone

(E/Z)- oxacyclohexadec-11- en-2-one

(Z)-oxacyclotridec-10- en-2-one

(E/Z)- oxacycloheptadec-11- en-2-one

(Z)-oxacyclotetradec- 11-en-2-one

7-Ambrettolide

(Z)-oxacyclotetradec- 10-en-2-one

Habanolide

(Z)-oxacyclopentadec- 11-en-2-one

Nirvanolide

(Z)-oxacyclohexadec- 11-en-2-one

Cyclopentadecanolide (exaltolide)

(Z)-oxacycloheptadec- 11-en-2-one

Cyclopentadecanone (exaltone)

(E/Z)- oxacyclotetradec-10- en-2-one

Ethylene brassylate

(E/Z)- oxacyclopentadec-11- en-2-one

Cyclohexadecanone

EXPERIMENTAL General Information—Materials and Methods

Exemplary embodiments provided in accordance with the presently disclosed subject matter include, but are not limited to, the claims and the following embodiments.

Unless otherwise specified, all manipulations were carried out under air-free conditions in dry glassware in a Vacuum Atmospheres Glovebox filled with N₂. General solvents were purified by passing through solvent purification columns. Commercially available substrates were used as received. All solvents and substrates were sparged with Ar before bringing into the glovebox and filtered over neutral alumina (Brockmann I) prior to use. The olefin metathesis catalysts used in the following examples, were synthesized according to the procedures described in International Patent Applications PCT/US2017/046283 and PCT/US2018/027098.

Kinetic NMR experiments were performed on a Varian 600 MHz spectrometer with an AutoX probe. Spectra were analyzed using MestReNova Ver. 8.1.2. ¹H and ¹³C NMR characterization data were obtained on a Bruker 400 with Prodigy broadband cryoprobe and referenced to residual protio-solvent.

All reactions involving metal complexes were conducted in oven-dried glassware under an argon or nitrogen atmosphere using standard Schlenk techniques. Chemicals and solvents were obtained from Sigma-Aldrich, Strem, Alfa Aesar, Nexeo, Brenntag, AG Layne and TCI. Commercially available reagents were used as received unless otherwise noted. Silica gel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

The following abbreviations are used in the examples:

mL milliliter

L liter

° C. degrees Celsius

CD₂Cl₂ deuterated dichloromethane

CDCl₃ deuterated chloroform

C₆D₆ deuterated benzene

Ar argon

HCl hydrochloric acid

KHMDS potassium bis(trimethylsilyl)amide

r.t. room temperature

THF tetrahydrofuran

NaHCO₃ sodium bicarbonate

Et₂O diethylether

HCl hydrochloric acid

MgSO₄ magnesium sulfate

DCM dichloromethane

Example 1 Synthesis of C738ss

To a 20 mL scintillation vial equipped with a magnetic stir bar was added C747 (0.200 g, 0.268 mmol), dichloromethane (5 mL), and 3-hexene (0.066 mL, 0.536 mmol). The reaction was stirred for 30 minutes then (3,6-dichlorobenzene-1,2-dithiolato) (ethylenediamine)zinc(II) (0.099 g, 0.295 mmol) and THF (5 mL) were added and the reaction stirred for an additional 30 minutes before removing all volatiles in vacuo. The resulting residue was extracted with dichloromethane (5 mL), passed through a syringe filter, then slowly combined with diethyl ether (30 mL) to afford a brown microcrystalline solid. The solid was isolated by filtration, washed with diethyl ether (1×10 mL) followed by hexanes (1×10 mL) then dried in vacuo to afford C738ss (0.132 g, 66.9% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 14.77 (dd, J=7.1, 3.6 Hz, 1H), 7.06 (d, J=8.2 Hz, 1H), 7.05 (br s, 1H), 7.03 (br s, 1H), 6.96 (d, J=8.2 Hz, 1H), 6.92 (br s, 1H), 6.83 (br s, 1H), 4.05-3.90 (m, 6H), 2.85 (s, 3H), 2.76 (s, 3H), 2.58 (s, 3H), 2.53 (s, 3H), 2.28 (br s, 6H), 2.24 (s, 3H), 2.08 (s, 3H), 0.35 (t, J=7.5 Hz, 3H).

Example 2 Synthesis of (Z)-4-Hexen-7-octenoate

To a 100 mL round-bottom flask charged with a stir bar were added 50 mL dichloromethane, 7-octenoic acid (1.54 mL, 10.0 mmol) and pyridine (80.7 μL, 1.00 mmol). Oxalyl chloride (1.00 mL, 11.8 mmol) was added dropwise, and the reaction was stirred for overnight. Solvents were then removed in vacuum. 20 mL dichloromethane and pyridine (0.81 mL, 10.0 mmol) were added, and cis-4-hexenol (1.09 mL, 9.3 mmol) was subsequently added dropwise at 0° C. After bringing the reaction to room temperature, it was stirred for an additional 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (1.58 g, 76% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 3 Synthesis of (Z)-3-Hexenyl 9-decenoate

To a 100 mL round-bottom flask charged with a stir bar were added 50 mL dichloromethane, 9-decenoic acid (1.85 mL, 10.0 mmol) and pyridine (80.7 μL, 1.00 mmol). Oxalyl chloride (1.00 mL, 11.8 mmol) was added dropwise, and the reaction was stirred for overnight. Solvents were then removed in vacuum. 20 mL dichloromethane and pyridine (0.81 mL, 10.0 mmol) were added, and cis-3-hexenol (1.10 mL, 9.3 mmol) was subsequently added dropwise at 0° C. After bringing the reaction to room temperature, it was stirred for an additional 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (2.02 g, 86% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 4 Synthesis of (Z)-3-Hexenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mL dichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine (0.89 mL, 11.0 mmol). Cis-3-hexenol (1.18 mL, 10.0 mmol) was then added dropwise at 0° C. The reaction mixture was brought to room temperature and stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (2.53 g, 95% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 5 Synthesis of (Z)-4-Hexenyl 9-decenoate

To a 100 mL round-bottom flask charged with a stir bar were added 50 mL dichloromethane, 9-decenoic acid (1.85 mL, 10.0 mmol) and pyridine (80.7 μL, 1.00 mmol). Oxalyl chloride (1.00 mL, 11.8 mmol) was added dropwise, and the reaction was stirred for overnight. Solvents were then removed in vacuum. 20 mL dichloromethane and pyridine (0.81 mL, 10.0 mmol) were added, and cis-4-hexenol (1.09 mL, 9.3 mmol) was subsequently added dropwise at 0° C. After bringing the reaction to room temperature, it was stirred for an additional 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (2.05 g, 87% yield). The H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 6 Synthesis of (Z)-4-Hexenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mL dichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine (0.89 mL, 11.0 mmol). Cis-4-hexenol (1.17 mL, 10.0 mmol) was then added dropwise at 0° C. The reaction mixture was brought to room temperature and stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (2.45 g, 92% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 7 Synthesis of (Z)-5-Octenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mL dichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine (0.89 mL, 11.0 mmol). Cis-5-octenol (1.51 mL, 10.0 mmol) was then added dropwise at 0° C.; the reaction mixture was brought to room temperature and stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (2.82 g, 96% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 8 Synthesis (Z)-6-Nonenyl 10-undecenoate

To a 100 mL round-bottom flask charged with a stir bar were added 20 mL dichloromethane, undecenoyl chloride (2.37 mL, 11.0 mmol), and pyridine (0.89 mL, 11.0 mmol). Cis-6-nonenol (1.67 mL, 10.0 mmol) was then added dropwise at 0° C. The reaction mixture was brought to room temperature and stirred for 4 h. The reaction mixture was extracted with 1M aq. HCl (200 mL) and sat. aq. NaHCO₃ (200 mL). The organic layer was dried over anhydrous MgSO₄, filtered, and solvents were removed in vacuum. The product was purified by column chromatography on silica gel (5:95 Et₂O: pentane) to yield a colorless oil (2.74 g, 89% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 9 Synthesis of (Z)-Oxacyclododec-8-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added (Z)-4-hexenyl-7-octenoate (21.0 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C785ss (4.4 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (12.0 mg, 70% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 10 Synthesis of (Z)-Oxacyclotridec-10-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added (Z)-3-hexenyl 9-decenoate (23.7 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C869ss (4.9 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (12.5 mg, 68% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 11 Synthesis of (Z)-Oxacyclotetradec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added (Z)-3-hexenyl 10-undecenoate (25.0 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C725ss (4.1 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (13.2 mg, 67% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 12 Synthesis of (Z)-Oxacyclotetradec-10-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-4-hexenyl 9-decenoate (23.7 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C738ss (4.2 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (14.2 mg, 72% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 13 Synthesis of (Z)-Oxacyclopentadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-4-hexenyl 10-undecenoate (25.0 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C785ss (4.4 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (15.6 mg, 70% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 14 Synthesis of (Z)-Oxacyclohexadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-5-octenyl 10-undecenoate (27.6 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C869ss (4.9 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (17.7 mg, 79% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 15 Synthesis of (Z)-Oxacycloheptadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-6-nonenyl 10-undecenoate (28.9 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C725ss (4.1 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 1 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (17.8 mg, 75% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

For determining selectivity, Z/E mixtures of lactones were synthesized using C647m as references for GC and ¹³C NMR studies for comparison. The macrocyclic lactones synthesized herein are obtained in Z/E ratios from 95/5 to 99/1.

Example 16 Synthesis of (E/Z)-Oxacyclotetradec-10-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-4-hexenyl 9-decenoate (23.7 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C647m (4.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 4 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (13.0 mg, 67% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 17 Synthesis of (E/Z)-Oxacyclopentadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-4-hexenyl 10-undecenoate (25.0 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C647m (3.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 4 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (11.7 mg, 52% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 18 Synthesis of (E/Z)-oxacyclohexadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-5-octenyl 10-undecenoate (27.6 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C647m (3.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 4 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (16.8 mg, 75% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature.

Example 19 Synthesis of (E/Z)-Oxacycloheptadec-11-en-2-one

To a 150 mL Schlenk tube equipped with a stir bar is added a solution of (Z)-6-nonenyl 10-undecenoate (28.9 mg, 0.0938 mmol) in 30.3 mL DCM and a solution of C647m (3.6 mg, 0.00563 mmol) in 1 mL DCM. The tube is sealed and taken out of the glovebox. After one freeze, pump, thaw cycle, the reaction flask is heated at 40° C. for 4 h and then quenched with 1 mL butyl vinyl ether. Solvents are removed in vacuum, and the product is purified by column chromatography on silica gel (1:49 Et₂O: pentane) to yield a colorless oil (16.4 mg. 69% yield). The ¹H NMR and ¹³C NMR data correspond to the data found in the literature. 

The invention claimed is:
 1. An olefin metathesis catalyst represented by the structure of Formula (5),

wherein: R¹ is hydrogen; R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; or R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide with the sulfoxide group; X¹ and X² are independently Cl, Br, F or I; R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; and R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl.
 2. The olefin metathesis catalyst according to claim 1, selected from:


3. An olefin metathesis catalyst represented by the structure of Formula (8)

wherein: R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group; R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3 ,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen and R¹⁴ is hydrogen; R^(x) is methyl, hydrogen or Cl; R^(y) is hydrogen; R^(w) is hydrogen; R^(z) is Cl, t-butyl, hydrogen or phenyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.
 4. The olefin metathesis catalyst according to claim 3, selected from:


5. A method for synthesizing a musk macrocycle, represented by Formula (A):

comprising, performing a ring closing metathesis reaction on a diene of Formula (E)

wherein: R^(e) is H, methyl, ethyl, or propyl; p is 1, 2, 3, or 4; q is 4, 5, 6, or 7; in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of Formula (4):

wherein: M is a Group 8 transition metal; L² is a neutral electron donor ligand; n is 0 or 1; m is 0; R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R^(a) and R^(b) are linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group; X¹ and X² are independently anionic ligands; R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; X⁵ and Y⁵ are independently C, CR^(3A) or N; and only one of X⁵ or Y⁵ can be C or CR^(3A); R^(3A) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or —[CR¹¹═CR¹³]—; R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; “s” and “t” are independently 1 or 2; R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; and R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.
 6. The method according to claim 5, wherein the olefin metathesis catalyst is represented by the structure of Formula (5),

wherein: R¹ is hydrogen; R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; or R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide with the sulfoxide group; X¹ and X² are independently Cl, Br, F or I; R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl; and R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl or 2-methyl-phenyl.
 7. The method according to claim 6, wherein the olefin metathesis catalyst is selected from:


8. The method according to claim 5, wherein the olefin metathesis catalyst is represented by the structure of Formula (8)

wherein: R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^(a) and R^(b) are linked together to form a five or a six-heterocyclic membered ring with the sulfoxide group; R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3 ,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl or 2-methyl-phenyl; R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen and R¹⁴ is hydrogen; R^(x) is methyl, hydrogen or Cl; R^(y) is hydrogen; R^(w) is hydrogen; R^(z) is Cl, t-butyl, hydrogen or phenyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.
 9. The method according to claim 8, wherein the olefin metathesis catalyst is selected from: 